Packaged anti-plaque oral compositions

ABSTRACT

An oral composition, such as a paste or gel dentifrice or a liquid mouthwash, containing a substantially water insoluble non-cationic antibacterial agent, such as triclosan, which, when used to clean the teeth or rinse the mouth, acts to decrease plaque on the teeth, is packaged in a dispensing container or bottle which includes a solid polymeric material, such as polyfluoroethylene, which is compatible with the antibacterial agent so that excessive loss of anti-plaque activity of such agent on storage is avoided. Alternatively, various other polymers may be employed as container parts, which normally would cause excessive losses of anti-plaque action of the antibacterial agent in the composition but such action is countered by the presence of a stabilizer, such as a terpene, e.g., limonene, in the oral composition formula. Also described is a method for inhibiting development of plaque on teeth.

This is a division, of application Ser. No. 07/427,660 now U.S. Pat. No.5,135,738 filed Oct. 26, 1989 which is a continuation-in-part of each ofU.S. patent applications Ser. Nos. 07/398,566, now U.S. Pat. No.5,032,386, 07/398,592, 07/398,605, 07/398,606 now U.S. Pat. No.4,991,901 and 07/399,669, now abandoned all of which were filed on Aug.25, 1989, and of Ser. No. 410,682, now abandoned filed Sep. 21, 1989 andall of which are continuations-in-part of Ser. No. 07/291,712, now U.S.Pat. No. 4,894,220, filed Dec. 29, 1988.

This invention relates to packaged anti-plaque oral compositions whichcomprise an anti-plaque antibacterial agent such as 2', 4,4'-trichloro-2-hydroxy-diphenyl ether (THDE), as an effectiveanti-plaque component, which compositions are packaged in a containerwhich includes a polymeric plastic material in contact with the oralcomposition, which plastic is compatible with the antibacterial agent inthe composition. Although various plastics may diminish the anti-plaqueaction of the mentioned antibacterial agents, certain plastics, such aspolyfluoroethylene and polyvinyl chloride, have been found to becompatible with THDE and it has been discovered that they do not causeexcessive losses of antibacterial and anti-plaque activities ofcontained oral compositions on storage, at room or elevatedtemperatures. Even when the contacting plastic part(s) of the containeris/are of a plastic which is not in itself entirely compatible with theantibacterial compound, compatibility can be improved by incorporatingin the oral composition a stabilizing proportion of a stabilizer for theantibacterial compound, such as a terpene, e.g., limonene, or anessential oil (natural or synthetic), which may be present in aflavoring material for the oral compositions. Such stabilizing materialis present in sufficient proportion so that the oral composition, aspackaged and dispensed, is an effective anti-plaque composition, theproduction of which is an object of this invention. Included within theinvention is a method of contacting oral surfaces with oral compositionscontaining effective proportions of anti-plaque agent. Also within theinvention is a toothbrush having on its bristles an effective proportionof an anti-plaque dentifrice.

Plaque on teeth is considered to be causative factors of negativeperiodontal conditions, and dental plaque is a precursor of calculi.Plaque may form on any part of the tooth surface, including the gingivalmargin. It makes the teeth appear dull and in addition to promotingdevelopment of calculi, it has been implicated in occurrences ofgingivitis. Therefore, oral compositions that contain anti-plaquecomponents which prevent or inhibit the development of plaque on theteeth are valuable dental care aids.

Although it has been known that antimicrobial agents in oralcompositions may reduce plaque, sometimes being especially effective incombinations with other materials, various such antibacterial compoundspossess disadvantageous properties which mitigate against theiremployment in such oral compositions. For example, cationicantibacterial compounds, such as quaternary ammonium halides, tend todiscolor the teeth and may be inactivated by the presence of anionicmaterials in the oral preparations (and often it will be desirable toemploy anionic surfactants or detergents in oral compositions).

Essentially water insoluble halogenated (and often hydroxylated)diphenyl ethers, such as THDE (triclosan) and2,2'-dihydroxy-54,5'-dibromo-diphenyl ether (DDDE), are effectiveanti-plaque antibacterial agents but can be inactivated by nonionicsurfactants and by many plastics, as has been discovered by applicants.Thus, an object of this invention has been to incorporate antibacterialanti-plaque agents, such as halogenated diphenyl ethers, particularlyTHDE and DDDE, and similar anti-plaque agents in oral compositions, andto store such compositions in and dispense them from packages orcontainers in which they will not lose an excessive proportion of theactivity of such antibacterial agent on storage, before intended use. Inprior art triclosan dentifrices, as delivered from the dispenser, thetriclosan delivery has not been in an effective amount to significantlyreduce plaque when employed once or twice daily at 1.5 g./use with oneminute brushings, which is considered to approximate normal brushingpractice. To be effective, such uses should result in at least 25%reduction in plaque after three weeks' use, compared to three weeks' useof a control toothpaste in the same manner.

The most preferred antibacterial anti-plaque component of the presentpackaged oral compositions is THDE, which is also known as triclosan.Such is disclosed in U.S. Pat. No. 4,022,880 as an antibacterial agent,in combination with an anticalculus agent (which provides zinc ions),and in German patent specification (OLS) No. 35 32 860 in combinationwith a copper compound. It is also disclosed in European patentapplications Nos. 0 161 898 and 0 161 899, and in European patentapplication 0 220 890 it is disclosed in dentifrices with polyethyleneglycol and oil based flavor.

Various oral compositions or dental preparations are known, includingpaste, gel, powder, liquid, tablet, lozenge, sachet and packeteddentifrices, liquid and tableted mouthwashes; and professionally appliedtooth treating agents (such as tooth hardening compositions, e.g.,fluoride solutions). Such products have been packed in deformable tubes,pump dispensers, pressurized dispensers, packets, bottles, jars andother containers. Although deformable or collapsible tubes wereinitially made of metals, such as lead and aluminum, and bottles weremade of glass, in recent years such containers have often been made ofsynthetic organic polymeric plastics or made of laminates which includedsuch plastics. Interactions between oral compositions and the materialsof containers in which they were packed have been known, such asreactions between toothpastes and aluminum containers, and to preventsuch reactions containers have been specially treated or differentcontainer materials have been employed. However, applicants do notbelieve that before their invention it had been known to the prior artthat some plastic packaging materials could adversely affect theanti-plaque activities of halogenated diphenyl ether antibacterialcompounds that had been incorporated in oral compositions and packed incontainers in which they came into contact with such plastics, nor dothey believe that it had been discovered that certain plastics could beemployed for such container parts without causing losses of theanti-plaque activities of halogenated diphenyl ethers or that losses ofsuch activities of oral compositions packed in contact with "reactive"plastics (which react with, absorb or otherwise reduce the antiplaqueactivity of the oral composition) could be inhibited or prevented byincorporating in the compositions terpenes, such as limonene, and othercomponents of flavors for oral preparations.

In accordance with certain of its aspects the present invention relatesto an oral composition containing an effective anti-plaque proportion ofa substantially water insoluble non-cationic antibacterial agent whendispensed, is packaged in a dispensing container which includes a solidpolymeric material, such as a synthetic organic polymeric plasticmaterial, in contact with the oral composition, which solid polymericmaterial is compatible with the antibacterial agent in the presence ofthe oral composition and does not cause excessive loss of antibacterialand anti-plaque activities of the oral composition on storage in thecontainer (such as at temperature in the range of 20° to 40° C. forseveral weeks, preferably up to a year or more). The packaged oralcomposition is usually a toothpaste, gel dentifrice or mouthwashcontained in a deformable dispensing tube, pump dispenser or bottle,respectively, having no plastic parts which adversely affect theanti-plaque action of the antibacterial agent, (which is preferably ahalogenated diphenyl ether, such as triclosan), or containing in theoral composition a component which inhibits or prevents any suchdetrimental "reaction" between the antibacterial agent and any plasticpart of the container which could otherwise adversely affect thecomposition's anti-plaque action.

BRIEF DESCRIPTION OF THE DRAWINGS

The invention will be readily understood from the description thereof inthis specification, taken in conjunction with the drawing, in which:

FIG. 1 is a perspective view of a toothpaste tube and its removed cap,with toothpaste having been squeezed from the tube onto a brush;

FIG. 2 is an enlarged partial sectional view of a laminated wall of asqueezable tube like that of FIG. 1;

FIG. 3 is a vertical sectional elevation of a pump dispenser forcontaining and dispensing toothpaste or dentifrice gel, as desired;

FIG. 4 is a side elevational view of a heat sealed sachet or pouchcontaining a single use amount of a toothpaste; and

FIG. 5 is an elevational view of a capped bottle of mouthwash.

In FIG. 1 packaged anti-plaque toothpaste article 11 includes deformabletoothpaste tube 13, which contains anti-plaque toothpaste 15, showndispensed in a unitary amount such as about 0.8 to 2 grams by squeezingonto brush 17. Tube 13 is opaque and is made of a synthetic organicpolymeric plastic material, such as polyfluoroethylene or is lined withsuch a material, as in a laminate, which does not adversely affect theanti-plaque activity of the toothpaste on storage. Alternatively, tube13 may be made of or lined with a plastic which has been found toadversely affect anti-plaque action of the toothpaste (by decreasing theanti-plaque action of antibacterial and anti-plaque halogenated diphenylether component of the toothpaste) but in such case the adverse effecton anti-plaque action is prevented or inhibited by the presence in thedentifrice of a stabilizing agent, which may be a terpene, e.g.,limonene, or other effective flavor components. Preferably neither thetoothpaste tube nor the cap 19 thereof nor any other part of the tubewhich may come into contact with the toothpaste (such as a liner for thecap) should be made of co-polyester/polyether elastomer or of otherplastic which substantially diminishes the anti-plaque action of theoral preparation, even in the presence of a stabilizer for theanti-plaque component. It is also considered to be desirable to avoidthe presence of other elastomers, such as isobutadienes,polychloroprenes, butadiene rubbers and nitrile rubbers, which mightreact with or absorb THDE. Desirably, such parts will be made ofplastics which do not adversely affect anti-plaque activity, even in theabsence of terpenes or other stabilizing agents in the dentifrice, butsuch other destabilizing plastics may be employed when such stabilizeris present in the toothpaste to counteract the inactivating effect ofthe plastic (except that elastomeric co-polyester/polyether and otheradverse elastomers will preferably be avoided).

In FIG. 2 there is shown a laminate of polyfluoroethylene film 21,aluminum sheet 23 and polyethylene film 25, with the polyfluoroethylenebeing on the inside of the tube wall, where it will be in contact withthe toothpaste. The liner, not shown, for the cap 19 of FIG. 1, may alsobe of polyfluoroethylene, so that all surfaces in contact with thetoothpaste during the storage are compatible with the halogenateddiphenyl ether antibacterial component of the toothpaste and do notpromote excessive losses of its anti-plaque activity on storage. Insteadof having the inner wall 21 of the laminate of polyfluoroethylene, itmay be of polyethylene and wall 21 may be of polyethylene or othersuitable polymer.

In FIG. 3 the pump dispenser for toothpaste is of a type marketed byGuala S.p.A., of Italy, which is the subject of U.S. Pat. No. 4,776,496.Pump dispenser 27, when ready for use, contains toothpaste incompartment 29, which is defined by bottom wall 31 and membrane 33.Depression of a actuating lever 35 causes a downward movement ofmembrane 33, forcing toothpaste through conduit 37 and out spout 39.When pressure on the actuating lever 35 is released membrane 33, whichis elastic, returns to its original configuration and moves conduit 37and lever 35 back to their initial positions. At the same time, bottom31 is pushed upwardly by atmospheric pressure. The various internalparts of the pump dispenser that contact the toothpaste are preferablyof plastic(s) that do not inactivate the halogenated diphenyl etherantibacterial and anti-plaque agent. However, in the event that it isnot feasible to utilize plastics that have the necessary physicalproperties for the various contacting parts and still are compatiblewith the anti-plaque agent other plastics may be employed, providingthat the toothpaste composition (or gel dentifrice) includes astabilizing substance, such as limonene or other operative terpene orflavor component. However, it is considered best to avoid employing anyco-polyester/polyether elastomers, especially for the pumping membrane(33), which plastic appears to be especially active against THDE in oralcompositions of the types described.

In FIG. 4 sachet, pouch or packet 41 is shown as a heat sealed unit,with heat sealing about three sides thereof, represented by numerals 43and 45. The fourth side 47 is merely folded back on itself and need notbe heat sealed. Inside the sealed packet is an oral composition, such astoothpaste, not shown, and the interior surface of such sachet is of aplastic material which does not promote excessive loss of anti-plaqueaction of the antibacterial compound of the contained oral composition.As with the other containers for the anti-plaque oral compositions,laminates may be utilized, with a plastic layer on the interior thereofwhich does not adversely affect the antibacterial agent, or when theplastic does have such a negative affect, it may be counteracted by thepresence in the oral composition of a suitable stabilizer, which ispreferably also useful as a flavoring agent thereof.

In FIG. 5 is shown an opaque bottle 49 having sealing cap 51 thereon.Both the bottle and the sealing insert (not shown) in the cap are ofplastic materials which are compatible with the THDE that is theanti-plaque component in the mouthwash 53 contained in the bottle. As inthe other examples given, when a "reactive" plastic is employed as thematerial of the inner portion of the bottle or of the cap seal asuitable stabilizer will be present in the mouthwash to preventexcessive loss of anti-plaque action of the THDE or other halogenateddiphenyl ether.

In addition to the compositions described as being present in theillustrated packages, which include gel dentifrices and thick liquidsinstead of toothpastes, there may also be incorporated in such packagestooth treating compositions suitable for professional use, such as toothhardeners, which may include fluorides and phosphates, compoundedantibacterial agents, plaque-indicating dye solutions and other suitableoral compositions. Also, pressurized or "aerosol" compositionscontaining the mentioned anti-plaque compounds may be packed inpressurized containers (usually pressurized with gaseous nitrogen)providing that contacting plastic parts of such containers are ofmaterials which do not cause excessive losses of anti-plaque propertiesof the anti-plaque agent in the contained toothpastes or other oralcompositions.

In addition to the various containers illustrated in the drawing andmentioned above there may also be employed squeeze bottles, capsules,jars, sponge-like media and various types of mechanical dispensingcontainers. Because some of the halogenated diphenyl ether antibacterialcompounds are photosensitive it will sometimes be desirable for suchcontainers to be composed of, coated or laminated with a chemical orphysical light screening material, many of which are known, to preventtransmission to the oral composition and to the anti-plaque compound ofany inactivating radiation, e.g., ultraviolet light. Also, suchcontainers will often desirably be opaque to prevent such actinicradiation from inactivating the anti-plaque component of the containedoral preparation, such as a toothpaste.

The cause(s) of inactivation by plastics of THDE and other substantiallynon-cationic antibacterial agents that have anti-plaque properties inoral compositions has/have not yet been established. Research to datahas not pinpointed the mechanism responsible for losses of suchdesirable activity but so far the results do not conclusively point toeither chemical reactions or physical absorptions. Tests of basicmouthwash or mouth rinse formulations containing THDE show that whensuch a mouthwash or mouth rinse is aged in dispensing containers at roomtemperature, 38° C. and 49° C., for up to twelve weeks, there are"excessive" losses (over 25% of the initial concentration of THDE) whenthe mouth rinse has been in contact with such container walls and partsof low density polyethylenes, high density polyethylenes, polyethyleneterephthalates, polypropylenes, nylons, polyallomers andpolymethylpentenes. Similarly, high losses result when such storage isin containers with inner walls or parts of co-polyester/polyetherelastomers, such as those which have previously been employed in Gualapump membranes. It was found that polyfluoroethylenes, such aspolytetrafluoroethylenes, polyvinyl chlorides, polycarbonates andpolysulfones did not absorb or react with excessive proportions of theTHDE. However, polycarbonates and polysulfones are brittle and henceoften are unsuitable for employment as dispensing container parts.Polyvinyl chlorides sometimes impart a foreign taste to oralcompositions, such as toothpastes, and therefore will often be avoidedas a container material, except in certain cases where such taste iscompatible with the taste of the toothpaste flavoring employed. Thus, ofall the polymeric plastic materials available, polyfluoroethylene isespecially identified as a feasible material for use in the presentcontainers or packages which does not seriously diminish the anti-plaqueactivity of the anti-plaque agents. However, as was indicatedpreviously, by incorporating in the oral compositions stabilizingcompounds for the anti-plaque agents, such as terpenes, of whichlimonene is representative, essential oils (which often containterpenes), and other flavor components with similar "stabilizing"properties, one is able to reduce the activity losses of the antiplaqueagents when they are in contact with containers or container parts madeof the various mentioned polymeric plastics with which excessive lossesin antiplaque activity occur. Therefore, one need not be dependent onpolyfluoroethylene as a container dispenser material, providing that theoral composition also contains a stabilizing proportion of terpene orother suitable "stablizer". When such stabilizer is present in the oralcompositions or when polyfluoroethylene (or polyvinyl chloride,polycarbonate or polysulfone) is the only polymeric plastic in contactwith the oral composition, storage losses of anti-plaque activity areless than 25%, and preferably will be less than 10%, even after ambiantto relatively high temperature storage, for example 20° to 40° C., forperiods of time of several weeks to up to a year or more. It isconsidered that the most stable oral compositions are those whichinclude a stabilizing proportion of terpene or other suitable stabilizerand also include contacting container parts only of polyfluoroethylene(or any of the other unreactive plastics). Although the terpenes andessential oils are the primary stabilizers according to the presentinvention, other flavor components may also contribute to thestabilization of the anti-plaque material, either by interfering withany destabilizing reaction or by inhibiting absorption of thehalogenated diphenyl ether by the plastic (or by other unknownmechanism). Thus, it has been theorized that some components of the oralcompositions that tend to solubilize the THDE can act to maintain it inthe oral composition and inhibit or prevent its migration into theplastic. On the other hand, it has also been theorized that such asolubilizing action could promote migration of the solubilized THDE intothe plastic. Because the issue has not been resolved applicants are notbound by either theory. Also, while it is desirable for the terpenes andother stabilizers to be flavor components, that is not necessary, andthe stabilizers may be useful for only a stabilization purpose.

Although it is preferred that the package of this invention includeinternal walls (in contact with the compositions) of or lined with solidsynthetic organic polymeric plastic material, it is within the inventionto utilize other solid (and/or film-forming) polymeric materials,whether or not they are synthetic, organic or even plastic. Thus,polyethylene glycols and methoxypolyethylene glycols, such as those ofthe Carbowas® type, e.g., Carbowax 4,000 and Carbowax 6,000, may beemployed, often as lining materials in dispensing containers of thedescribed compositions. Inorganic silicon polymers, such as siloxanes,and non-synthetic organic film-forming materials, such as gums, e.g.,carrageenan, tragacanth, karaya, are also useful as liners fordispensers. Additionally solid polymeric materials, such as celluloseand starch and derivatives thereof, are also useful as containermaterials in contact with the contained antibacterial and antiplaquecomponents of the present packaged oral compositions.

The various oral packaged compositions of this invention that are mostfrequently made are toothpastes, dentifrice gels and mouthwashes(sometimes called mouth rinses). The former two will be referred toherein as dentifrices and the last will usually be called mouthwashes.Dentifrices comprise three major groups of components, the vehicle,polishing material and surfactant (or detergent). The antibacterialagent, e.g., halogenated diphenyl ether, is normally present in thevehicle, which vehicle usually comprises about 10 to 80% (all figuresare on a final composition basis) of the dentifrice. Of the vehicle,about 3 to 40% will be water, about 7 to 77% will be humectant, such asglycerol, sorbitol, propylene glycol or mixtures thereof and 0.5 to 10%will be gelling agent, such as sodium carboxymethyl cellulose. Irishmoss, iota carrageenan or hydroxyethyl cellulose or the like includingmixtures thereof. The polishing material of the dentifrice will normallybe from about 10 to 75% thereof in a gel or toothpaste or about 50 to99% in a powder and such polishing material may be colloidal silica,precipitated silica, sodium aluminosilicate, insoluble sodiummetaphosphate, hydrated alumina, calcined alumina, dicalcium phosphatedihydrate, anhydrous dicalcium phosphate or calcium carbonate, otherknown materials, or mixtures thereof. The surfactants include anionic,nonionic, cationic and zwitterionic surfactants but often the employmentof nonionic surfactant is avoided because of its adverse affect on theantibacterial compounds, e.g., THDE, and the employment of cationic andzwitterionic surfactants are also often avoided because they tend tostain or darken the teeth. Thus, synthetic organic anionic surfactants,which are also detergents, are the preferred cleaning agents in thedentifrices, and of these, sodium lauryl sulfate and other sodium higheralkyl sulfates of 10 to 18 carbon atoms in the alkyl groups thereof arepreferred, although various other well known sulfated and sulfonateddetergents may be substituted for them, at least in part. Other activeingredients, such as fluoride-providing compounds, e.g., sodium fluorideor sodium monofluorophosphate, may be present to harden the teeth,usually in proportions providing about 0.001 to 1% of fluoride to thecomposition, and adjuvants, such as flavoring and sweetener, inproportions of 0.1 to 10%, may be utilized. Additionally, it may bedesirable to employ a polycarboxylate, such as polyvinyl methyl ethermaleic anhydride (PVM/MA) copolymer (Gantrez®) in an amountcorresponding to about 0.5 to 4% of the dentifrice. Such polycarboxylatematerial has been found substantially to improve the anti-plaque actionof the antibacterial compound. Use of such polycarboxylates in oralcompositions is described in U.S. Pat. No. 4,627,977, which descriptionis incorporated herein by reference.

In mouthwashes the oral vehicle is preferably aqueous and alcoholic,with the alcohol being ethanol or isopropanol. The vehicle will normallybe 90 to 99.9% of the composition, of which the alcohol is 5 to 30% andpropylene glycol is often 2 to 10%, on a final product basis. Theremainder of the composition, 0.1 to 10%, may include flavor,surfactant, sweetener, colorant, anti-plaque agent and other adjuvantsfor specific purposes. In dentifrice and mouthwash compositions theeffective amount of antibacterial anti-plaque compound(s) will normallybe in the range of 0.02 to 0.2% more preferably 0.03 to 0.1% inmouthwashes, and normally about 0.25 to 1%, more preferably 0.25 to 0.5or 0.6% in dentifrices, with the proportion ranges not exceeding 0.8%for THDE in toothpastes and not exceeding 0.2% THDE in mouthwashes(because of possible mouth numbing effects at higher concentrations),and not being less than indicated in order to avoid ineffectivenessagainst plaque at low concentrations. Preferably the dispensedcompositions will contain proportions of the anti-plaque agent and THDEwithin the given ranges but when the initial concentration thereof iswithin the given range a loss of up to 25% may be acceptable and suchdispensed compositions are within the scope of the invention.

To stabilize oral compositions that are to be packaged in containerscontaining plastic walls or other parts, wherein the plastics are thosewhich are "reactive" with the antibacterial compounds, 0.01 to 2% ofterpene(s) or stabilizer(s) will desirably be present in the oralcompositions, preferably 0.05 to 1% and more preferably 0.1 to 0.5%.Such stabilizers may be present in a suitable flavoring agent for thedentifrice, if desired (and it often is), and will be at least 5% of theflavor, preferably at least 10%, more preferably at least 25% and mostpreferably at least 50%.

Although the above description is primarily relevant to dentifrices andmouthwashes, other oral compositions (e.g., including chewing gums) ofthe invention will contain similar proportions of components, dependingon the form of the composition (liquids containing less, as in the mouthrinses, and thicker compositions containing more as in the toothpastes),often with the additions of specific agents for accomplishing thepurposes of such compositions. Thus, tooth hardening compositions mayinclude fluorides and phosphates, such as sodium or potassium fluorideand sodium fluorophosphate, in either dentifrice or mouthwash bases,often in percentages in the range of 1 to 5%. Plaque-indicating dyesolutions may include a suitable dye (red is apparently the most favoredcolor for such products), often at a concentration in the range of 0.001to 0.1% in a mouthwash base. The compositions of the other products willbe adjusted accordingly, as will be known to those of skill in the art.

The antibacterial agent is a non-cationic material which is waterinsoluble or essentially water insoluble (having a solubility in waterat 25° C. of less than 10 g./l., and sometimes less than 1 or 0.1 g./l.)Such materials are soluble or dispersible in dentifrice vehicles thatcontain glycerol, sorbitol and/or propylene glycol, and in finalproducts based on such media. They are also soluble or dispersible inthe aqueous alcoholic media of mouthwashes.

Of the antibacterial agents, the halogenated diphenyl ethers willnormally contain bromine and/or chlorine, with chlorine being thepreferred halogen. They will preferably by substituted with 1 to 3hydroxyls and 1 to 4 halogens. More preferably they will be substitutedwith 1 or 2 hydroxyls and 2 or 3 halogens, preferably with foursubstituents, two on each ring. Among the more preferred of suchcompounds are 2, 2'-dihydroxy-5,5'-dibromo-diphenyl ether and 2', 4,4'-trichloro-2-hydroxy-diphenyl ether, with the latter compound (THDE)being most preferred. Various replacement halogenated phenolic,non-cationic, substantially water insoluble antibacterial anti-plaquecompounds, such as those itemized at pages 2-8 of application Ser. No.07/398,566, filed Aug. 25, 1989, which application is incorporatedherein by reference, will be substituted in whole or in part for thehalogenated diphenol ethers, when that is considered to be appropriate.

The terpenes, which term, for the purpose of this specification,includes the terpene hydrocarbons and oxygenated derivatives thereof,include such compounds as dl-limonene, menthol, diterpenes, polyterpenesand derivatives thereof, many of which are found in various essentialoils and other flavors. In addition to being useful as stabilizers forhalogenated diphenyl ethers they often contribute desirable flavors tothe present oral compositions. Of the terpenes and their derivatives itis considered that limonene best balances these properties, althoughother terpenes, including those which are not flavors, are also useful,as are other emulsifiable lipophilic essential oils and flavoring agentswhich contain stabilizing components.

The various plastics that were previously described as the components ofcontainer and/or dispenser parts have been described only brieflybecause it is considered that their chemical natures and degrees ofpolymerization are well known, so detailing thereof is unnecessary inthis specification. If further details are wanted reference should bemade to Modern Plastics Encyclopedia, which is published on an annualbasis by McGraw-Hill Inc., New York, N.Y.

As was described in incorporated Ser. No. 07/398,566 the compositions(of the invention) may contain a source of fluoride ions, capable ofsupplying 25 to 5,000 ppm of fluoride ion in the oral cavity, preferably300 to 2,000 ppm and more preferably 800 to 1,500 ppm. See incorporatedU.S. Pat. No. 4,627,977 for further details about suitable fluorides,proportions and manufacturing details. The fluoride acts primarily as atooth hardener but also serves to stabilize polyphosphate anti-calculuscompound when present. Such polyphosphate is preferably a mixture ofsodium and potassium pyrophosphates and it is also stabilized byGantrez® S-97. Proportion ranges are given in U.S. Ser. No. 07/398,605,filed Aug. 25, 1989, which application is incorporated herein byreference, and in incorporated U.S. Pat. No. 4,627,977 and U.S. Pat. No.4,806,340, which is incorporated herein by reference.

For other details of formulations, components, adjuvants, manufacturingsand uses, see the patent, specifications and applications previouslymentioned in this specification, which are hereby incorporated byreference.

Manufacture of the described oral compositions is by any of variousstandard techniques for producing such classes of compositions.Referring to specific examples for simplicity, the THDE is dispersedand/or dissolved in the vehicle portion of the dentifrice and theterpene is present in the flavoring agent. To make a dentifrice, thevehicle is prepared containing glycerol, sorbitol, and propylene glycol,gelling agents and suitable adjuvants (including Gantrez® S-97) andtriclosan), and the vehicle and aqueous anionic detergent (preferablysodium lauryl sulfate or a mixture of sodium lauryl sulfate and sodiummethyl cocoyl taurate) solution are mixed, followed by blending in ofthe polishing agent component with the pre-mix. Finally, flavoringagent, including terpene, dissolved in ethanol, is admixed and the pH isadjusted. To make the mouthwash the various components thereof aremerely admixed into the alcohol or aqueous alcoholic medium and arestirred until dissolved. A mix of sodium lauryl sulfate (SLS) and sodiummethyl cocoyl taurate (of a ratio in the range of 1:4 to 4:1) ispreferably employed as the anionic surfactant component of themouthwash, with the presence of the taurate permitting a correspondinglydesirable decrease in the SLS content, which is desirable. Other oralcompositions are prepared according to similar relevant procedures.

In packaging of the oral composition into the dispensing containers, itwill be desirable to avoid contacting of the compositions with plasticparts of co-polyester/polyether elastomer and it will also be desirableto avoid contacting of any compositions not containing stabilizing agent(such as terpene or flavor containing it) with plastic parts made ofthose plastics previously listed in this specification as reactive withTHDE and other such antibacterial and anti-plaque compounds. It will beespecially important to avoid the mentioned plastic parts for holdingtanks or any other containers, piping, pumps or equipment in which theoral composition may be held for any appreciable length of time or heldfor shorter lengths of time at elevated temperatures.

Even when the packaged compositions of this invention are prepared andcontacts of the oral compositions containing THDE or other halogenateddiphenyl ether antibacterial composition with the reactant plastics areavoided it will still be desirable to minimize exposures of suchpackaged compositions to heat and to light, both of which have beenfound to accelerate loss of anti-plaque activity. Thus, the inventedcompositions are preferably stored and packaged in opaque containers anddispensers at a temperature in the range of 10° to 38° C. and are storedat such a temperature, too. Otherwise, the packaged compositions may bestored and used in normal manner and the desirable anti-plaque effectsthereof will be obtained. Such effects have been verified by laboratorytesting and by evaluations of the teeth of volunteers serving on humanpanels, who employed the various packaged compositions and controls asdirected. Significant improvements in anti-plaque activities of thepackaged compositions of this invention are observed, compared tocontrol packaged compositions wherein the packaging included plasticparts that were "reactive" with the halogenated diphenyl etherantibacterial compound and which do not contain stabilizing agent in theoral composition. Such improvements are also found when packages made of"reactive" plastics (but not co-polyester/polyether elastomers) areemployed with oral compositions containing terpenes and are compared tocontrols in which the oral compositions contains no terpenes and noflavoring agents.

The following examples illustrate but do not limit the invention. Unlessotherwise indicated, all percentages and proportions in these examples,the specification and the appended claims are by weight, and alltemperatures are in °C.

EXAMPLE 1

    ______________________________________                                        Component                  Percentage                                         ______________________________________                                        Water, deionized           47.84                                              Sorbitol (70% aqueous solution)                                                                          20.00                                              Ethanol (95% aqueous solution)                                                                           12.50                                              Glycerol                   10.00                                              Propylene glycol           7.00                                               *Gantrez S-97 (13% solution)                                                                             1.92                                               Sodium hydroxide (50% aqueous solution)                                                                  0.12                                               Sodium lauryl sulfate      0.25                                               **Tauranol WSHP            0.20                                               ***Flavor Mixture          0.12                                               ****Triclosan (Irgasan ® DP 300, manufactured by                                                     0.05                                               CIBA-GEIGY)                                                                                              100.0                                              ______________________________________                                         *Polyvinyl methyl ether/maleic anhydride copolymer (GAF Corp.)                **Sodium methyl cocoyl taurate                                                ***Contains at least 25% terpenes, including at least 25% of limonene         ****THDE (2',4,4'-trichloro2-hydroxy-diphenyl ether)                     

The mouth rinse (or mouthwash) of this example is made by mixingtogether the various listed components in any suitable order, accordingto standard procedures, but preferably the triclosan is first dissolvedin the propylene glycol and ethanol mixture, after which it is mixedwith an aqueous solution of sorbitol, glycerol and the anionicsurfactants, with the flavor mixture being added last. The sodiumhydroxide solution is employed for neutralization of the resultingacidic mixture, which neutralization is to a pH of 6.84 (it beingdesirable to have the product at or near to a neutral pH).

The mouth rinse resulting is of excellent cosmetic stability and is ofacceptable flavor, and the flavor and triclosan are satisfactorilydissolved, with such dissolving being at least partially attributable tothe presence of the Tauranol WSHP. When only 0.25% of SLS is employed asthe anionic surfactant solubilizations of the flavoring agent andtriclosan are not as satisfactory. Although such solubilizations can beincreased by using more SLS the maximum acceptable limit of suchcompound in the mouth rinses is often about 0.25%, and the Tauranol®WSHP and SLS are safe and acceptable in the proportions employed. Thedescribed mouth rinse is tested in vitro for bioavailability oftriclosan against comparable mouth rinses of formulas omitting theTauranol WSHP, in one case, and replacing it with half as much of anonionic surfactant (Pluronic F-127) in another case. By triclosanuptake tests, measuring triclosan absorption by hydroxyapatite discsthat had been coated with saliva, and by protein absorption "zone ofinhibition" tests it is found that the presence of the mixed anionicsurfactant results in comparable bioavailability of triclosan, comparedto such availability from the SLS-only formula, and such availability issignificantly higher for the formulas containing no nonionic detergentthan for that wherein the nonionic detergent (Pluronic® F-127) ispresent.

The mouth rinse of the formula of this example is aged at elevatedtemperature (41° C.) for three and five weeks, which is consideredequivalent to at least about six months and one year's actual aging atroom temperature. Such aging tests are conducted in dispensingcontainers (bottles) made of glass, polyvinyl chloride and polyethyleneterephthalate (or lined with the plastic materials). Although chemicalanalyses of the mouth rinses after such aging periods find no losses oftriclosan when the container is glass, losses of triclosan from themouth rinses are noted when the containers are of polyethyleneterephthalate or of this sample of polyvinyl chloride but they aresignificantly less than a tolerable 25% (of the original concentration),and can be under 5 or 10%.

When, in place of the flavor mixture, dl limonene is employed in 0.1,0.2 and 0.4% quantities, even better stabilizations of the triclosan inthe described package dentifrices of the invention are obtainable, andsuch stabilizations also result when other terpenes from any of variousessential oils, and flavoring agents, are present in similarproportions. Such good results are also obtainable when the containermaterial or the liner thereof is of polymethyl pentene, polyallomer,polypropylene, high and low density polyethylenes, and nylon, althoughsuch materials, in the absence of the flavor mixture (and containedterpenes) cause significant and excessive losses of available triclosanfrom the mouth rinse on storage, especially at elevated temperatures.

EXAMPLE 2

    ______________________________________                                        Component         Percent                                                     ______________________________________                                        Water, deionized  84.42                                                       Ethanol (95%)     10.0                                                        Propylene glycol  5.0                                                         Sodium lauryl sulfate                                                                           0.50                                                        Triclosan         0.06                                                        Sodium saccharin  0.02                                                                          100.00                                                      ______________________________________                                    

A mouth rinse of the above formula is tested for triclosan availabilityafter storage for three weeks in dispensing containers made from orlined with various plastics. Testings are at room temperature, 38° C.and 49° C., with the elevated temperature storages simulating lengthierstorage times, up to a year or more at room temperature. Losses of over25% of the triclosan from the stored mouth rinse are noted when thecontainers are polymethyl pentene, polyallomer, polypropylene, high andlow density polyethylenes and nylon, with unacceptable results(excessive losses) being noted when the containers are polypropylene,polyethylene and nylon (with nylon being the worst).

When the container material or liner is polyvinyl chloride,polycarbonate, polysulfone or polyfluoroethylene, e.g.,polytetrafluoroethylene or Teflon®, essentially no losses of triclosanoccur. Losses of triclosan from mouth rinses stored in containers of orlined with the polymers mentioned (polymethyl pentene, etc.) may bedecreased in the same manner as described in Example 1 by incorporatingin the mouth rinse formula limonene, other terpenes, or essential oilsin which such may be present, with the proportion of terpene preferablybeing at least 0.1%, and more preferably being greater, e.g., 0.2% or0.4%, on a final composition basis. In some instances even theemployment of flavoring material which does not contain any significantproportion of terpenes will have a positive effect, although such effectwill not be expected to be as good as with terpenes in the formulation.

EXAMPLE 3

    ______________________________________                                        Component               Percent                                               ______________________________________                                        Propylene glycol        10.00                                                 Iota carrageenan        0.75                                                  Sodium fluoride         0.33                                                  Sorbitol (70%)          30.00                                                 Sodium saccharin        0.30                                                  Titanium dioxide        0.50                                                  Sodium hydroxide (50% aqueous solution)                                                               0.80                                                  Water, deionized        27.71                                                 +Luviform ™ (35% solution)                                                                         4.76                                                  ++Zeodent ™ 113      20.00                                                 +++Sident ™ 22S      2.00                                                  Sodium lauryl sulfate (94% active)                                                                    1.60                                                  Flavor                  0.95                                                  Triclosan               0.30                                                                          100.00                                                ______________________________________                                         +Polyvinyl methyl ether/maleic anhydride copolymer (BASF Corp.)               ++Silica polishing agent (J.M. Huber Corp.)                                   +++Silica thickening agent (Degussa Co.)                                 

A dentifrice of the above formulation is made in normal manner and isemployed as a medium for testing the stability of triclosan when thedentifrice containing it is exposed to different plastics which areemployed as materials of containers or of parts of the dispensers inwhich dentifrices are stored and from which they are dispensed. Theplastics for the tests are Pibiflex® 46, made by Inmont, and Arnitel®460 EM, mf'd. by AKZO, which are plastics that are employed as themembranes or bellows of a pump dispenser, as illustrated in FIG. 3. Sixsamples of plastics are tested, three of each of the mentioned plastics,with each of the three being treated with a different mold release agent(to determine whether the nature of the release agent is relevant to theproblem of triclosan stability in contact with plastics during storage).The release agents are Silicone Master™ (5% silicone oil and 95%polypropylene), Silicone Master plus Silicone Oil (with extra siliconeoil) and Armid O Master™ (5% oleo amide and 95% polypropylene),respectively. After two weeks storage of the test samples in contactwith the dentifrice at different temperatures (room temperature, 38° C.and 49° C.,), the dentifrice is removed from the plastic containermaterials and the plastics are washed with water and immersed inmethanol to dissolve any triclosan which might have been taken up bythem during storage. The methanol washings are collected and areanalyzed, using high performance liquid chromatography. It is found thatessentially the same types of absorptions of triclosan take place withthe different membrane materials and although there are variationsbetween them and such are somewhat dependent on the release agentsemployed, the results are essentially the same in all cases. Theco-polyester/polyether elastomers are found to absorb significantpercentages of triclosan from the dentifrice, which results areconfirmable when the co-polyester/polyether elastomers are used asbellows materials in pump dispensers containing the described dentifriceand other dentifrices within the invention. Accordingly, it isconsidered undesirable to employ co-polyester/polyether elastomers incontact with the present dentifrices or mouthwashes, even when thedentifrices and mouthwashes contain flavoring materials which includeterpenes (which are present in the flavoring of the dentifriceformulation), to the extent of at least 0.1% of the dentifrice.

When the tests are repeated, using actual Guala pump dispensers ascontainers for the dentifrices, with co-polyester/polyether elastomermembranes of Arnitel™, the losses of triclosan are also unacceptable butwhen the co-polyester/polyether elastomer is replaced by others of theacceptable plastics, e.g., polyfluoroethylene, the triclosan activity isimproved to within acceptable limits. Also, other plastic parts of suchpump dispensers, such as polypropylene inner walls thereof, are notfound to absorb excessive amounts of triclosan and do not seriouslydecrease the anti-plaque activity of the dentifrice, apparently due tothe presence of terpenes in the flavoring agent of the containeddentifrice.

A panel test is run, involving at least ten human subjects, who employthe dentifrice of this example, dispensed from polyethyleneterephthalate and polyethylene lined tubes, in twice-a-day brushings forone month, during which time plaque evaluations of the subjects' teethare made by trained observers. The test results establish that thedentifrice composition has a definite anti-plaque activity, similar tothat which is also observable in tests with the mouth rinses of Examples1 and 2, and also prove that the triclosan has not been unacceptablyinactivated, and still is present in an effective antibacterial andanti-plaque proportion in the dentifrice.

EXAMPLE 4

    ______________________________________                                        Component                   Percent                                           ______________________________________                                        Glycerol                    7.00                                              Propylene glycol            3.00                                              Iota carrageenan            0.75                                              Sorbitol (70%)              30.00                                             Sodium saccharin            0.30                                              Sodium fluoride             0.33                                              Titanium dioxide            0.50                                              Gantrez ® S-97 (13% solution)                                                                         15.00                                             Deionized water             16.07                                             Sodium hydroxide (50% aqueous solution)                                                                   0.80                                              Zeodent ® 113 (J.M. Huber Corp.)                                                                      20.00                                             Sylodent ® 15 (a silica thickener; W.R. Grace Corp.)                                                  3.00                                              Flavoring agent             0.95                                              Sodium lauryl sulfate       2.00                                              Triclosan                   0.30                                                                          100.00                                            ______________________________________                                    

A toothpaste of the above formula is made and is stored in Guala™ pumpdispensers having bellows membranes of the Arnitel type. The dentifriceis also filled into laminated tubes, having polyethylene terephthalateon the interior of the laminate, in contact with the dentifrice. Thedentifrices are aged at 5° C., 25° C., and 39° C., for two, four and sixweeks. After such aging periods, the dentifrices are dispensed at therate of about 1.5 grams per day and at weekly intervals the triclosancontents of the dispensed dentifrices are determined by analyses. In thecase of the Guala pump dispenser the dispensed dentifrice loses about27% of the triclosan, which is excessive and objectionable. The loss isabout constant, regardless of storage temperature or time of storage,which can be explained by absorption of the triclosan by the pumpmembrane, with which it is brought into contact prior to dispensing.Such membrane is of a co-polyester/polyether elastomer, which class ofplastics is to be avoided as a container material or as a part in acontainer or dispenser for dentifrices containing triclosan. However,when the elastomeric co-polyester/polyether membrane is replaced by onemade of any of the previously mentioned acceptable plastics, such aspolyethylene terephthalate, which can serve as membrane materials inmodified pump dispensers (modified to compensate for differentproperties of such plastics), triclosan stability is increased and thedispensed composition is satisfactory and effective as an anti-plaquetoothpaste.

Gel toothpaste formulations in such packages behave similarly withrespect to triclosan stability after storage and on dispensing.

In similar tests, using polyethylene terephthalate lined tubes littleloss (less than 5%) of triclosan is noted, indicating that the presenceof the terpenes (0.1% or more of the composition), including limonene,in the flavoring agent (or the flavoring agent itself) prevents loss ofthe triclosan or inactivation thereof. When polyfluoroethylene-linedtubes are employed there will be little loss of triclosan even when theflavoring agent is omitted from the dentifrice composition and such willalso be the case when polyvinyl chloride is employed as the linermaterial in contact with the dentifrice or when polysulfone orpolycarbonate package parts are in contact with such dentifrice.However, as was indicated previously, one will not usually employ suchthree last named plastics.

When in the reported test in which the dentifrice is dispensed from theGuala dispenser the Gantrez S-97 is replaced by 4.76 parts of Luviform(35%), with the difference being made up in deionized water, noappreciable difference in triclosan stability is noted between theformulas.

In the above formulas the polishing system is a siliceous system ratherthan one based on alumina. When the polishing agent is changed to analumina, the problems previously mentioned as having been noted withsome plastics are decreased but still exist. Also, the presences ofterpenes in the dentifrices promote triclosan stability, as suchpresences do in similar dentifrice compositions based on siliceouspolishing agents.

EXAMPLE 5

The mouth rinses and the dentifrices of the foregoing examples may bevaried in composition ±10% and ±25% for the various components thereof,providing that such percentages are not outside ranges given elsewherein this specification, and operative and effective antibacterial andanti-plaque products are obtainable, which are dispensable in effectiveanti-plaque state from the mentioned dispensing containers that are madeof compatible plastics. The products may also be modified by beingconverted to dentifrice gels, oral gels, pastes, liquids, lozenges,capsules, tablets, and sachets of the types previously mentioned in thespecification. Such products also will behave in similar manners, withthe triclosan or other halogenated diphenyl ether or antibacterialanti-plaque agent being sufficiently stable in the presence ofpolyfluoroethylene, polyvinyl chloride, polycarbonate and polysulfonepackaging or package component materials, even when no flavoring agentand no terpenes are present in the oral compositions, and being stablein the presence of polyethylenes, polypropylenes, polyethyleneterephthalates, polyallomers, nylons and polymethylpentenes, as packageor component materials, providing that a terpene, such as limonene, or astabilizing flavor component is present in the oral composition. As withthe other dentifrices and mouthwashes previously discussed, because ofexcessive absorption or other adverse action with respect to triclosanby co-polyester/polyether and other elastomers, uses of such materialswill preferably be avoided.

EXAMPLE 6

Dentifrices of the formulas of Examples 3 and 4 are made and aredispensed after one month's storage at 30° C. in collapsible toothpastetubes lines with polyethylene, in one case, and polyethyleneterephthalate, in another, onto bristled toothbrushes, as illustrated inFIG. 1. The amounts of toothpaste on the toothbrush are in the range of0.8 to 2.0 grams with 1 to 1.5 g. being preferred. When 1.5 g. isdispensed the active triclosan in the dentifrice on the brush is aboutfour milligrams (with only 10% of the triclosan being inactivated). Whenstorage is for a longer time or at a higher temperature or with a moredestabilizing plastic in contact with the dentifrice during storage thepackaged compositions can contain about 3 mg. of triclosan in the 1.5 gon the brush. Thus, with 1 g. of dentifrice on the brush the amounts oftriclosan will be about 2.7 mg. and 2 mg. respectively. For dentifricescontaining from 0.25 to 0.6% of triclosan the toothbrush can containfrom 2.2 to 8 mg. of triclosan if the triclosan inactivation is in the10 to 25% range, or up to about 9 mg. when no triclosan is inactivated.

The described packaged dentifrices are employed to brush the teeth withtypically about 0.8 to 2 g being dispensed onto toothbrushes for eachbrushing. Brushings are twice a day, morning and night, one minute at atime, for four weeks, after which definite improvement in anti-plaqueaction is apparent, compared to a control dentifrice that contains notriclosan. Improvement in anti-plaque action is also visible, comparedto an unflavored control (containing no terpene) that contains triclosanin a dentifrice package in polyethylene and polyethylene terephthalatelined tubes.

The present invention has been described with respect to illustrativeexamples and embodiments thereof but is not to be limited to thosebecause it is evident that one of skill in the art, with the presentspecification before him or her, will be able to utilize substitutes andequivalents without departing from the invention.

What is claimed is:
 1. A method of inhibiting plaque on teeth comprisingapplying to the teeth an oral composition dispensed from an articlecomprising a dispensing container having solid polyethylene orpolyethylene terephthalate polymeric material in contact with said oralcomposition in the container, which composition comprises an effectiveantibacterial antiplaque proportion of a substantially water insolublenoncationic halogenated diphenyl ether antibacterial antiplaque agentand a stabilizer to make said polymeric material compatible with saidagent in the presence of the oral composition, which compatibility issuch that after three weeks storage at elevated temperatures of at leastabout 41° C. less than about 25% of said agent is lost.
 2. A methodaccording to claim 1 in which the composition is a toothpaste, gel orliquid dentifrice, a liquid mouthwash, or a paste, gel or liquid toothtreating agent and in which the container is a deformable dispensingtube, a pump dispenser, a pressurized dispenser, or a sachet fortoothpaste, gel dentifrice, or paste or gel tooth treating agent, or abottle or other container for a liquid dentifrice, mouthwash or toothtreating agent.
 3. A method according to claim 2 in which thecomposition is a toothpaste, gel dentifrice or liquid mouthwash, andwherein the halogenated diphenyl ether antibacterial agent comprises adiphenyl ether substituted with 1-3 hydroxyls and 1-4 halogens selectedfrom the group consisting of chlorine and bromine, and in which thecontainer is a deformable dispensing tube, a pump dispenser or a sachetfor the toothpaste or gel dentifrice or is a bottle or other dispensingcontainer for the liquid mouthwash.
 4. A method according to claim 1wherein the halogenated diphenyl ether antibacterial agent comprises2',4,4'-trichloro-2-hydroxy-diphenyl ether (THDE) or2,2'-dihydroxy-5,5'-dibromodiphenyl ether (DDDE).
 5. A method accordingto claim 4 wherein the halogenated diphenyl ether antibacterial agentcomprises THDE.
 6. A method according to claim 4 in which thecomposition comprises 0.02 to 1% of THDE and/or DDDE.
 7. A methodaccording to claim 4 in which the composition comprises 0.02 to 1% ofTHDE.
 8. A method according to claim 4 in which the composition is aliquid mouthwash containing 0.03 to 0.1% of THDE and wherein the solidpolymeric material in contact with the oral composition in the containercomprises polyethylene.
 9. A method according to claim 4 in which thecomposition is a toothpaste or gel dentifrice containing 0.25 to 0.5% ofTHDE in a deformable dispensing tube, a pump dispenser or a sachet andthe solid polymeric material in contact with the oral composition in thecontainer comprises polyethylene.
 10. A method according to claim 4 inwhich composition is a toothpaste or gel dentifrice containing about0.3% of THDE and the container is a deformable dispensing tube or a pumpdispenser.
 11. A method according to claim 1 wherein the solid polymericmaterial which contacts the oral composition, comprises polyethylene.12. A method according to claim 1 wherein the solid polymeric materialin contact with the oral composition comprises polyethyleneterephthalate.
 13. A method according to claim 1 in which thecomposition contains a stabilizing proportion of a terpene or flavoringagent as the stabilizer.
 14. A method according to claim 8 wherein theliquid mouthwash contains a stabilizing 0.01 to 2% proportion of terpeneor flavoring agent as the stabilizer.
 15. A method according to claim 9wherein the toothpaste or gel dentifrice contains a stabilizing 0.01 to2% proportion of terpene or flavoring agent.
 16. A method according toclaim 13 wherein said polymeric material comprises polyethylene.
 17. Amethod according to claim 13 wherein said polymeric material comprisespolyethylene terephthalate.
 18. A method according to claim 13 whereinthe terpene content of the stabilizer is about 0.01 to about 2% of thecomposition.
 19. A method according to claim 16 wherein the terpenecontent of the stabilizer is about 0.01 to about 2% of the composition.20. A method according to claim 13 wherein the terpene content of thestabilizer is about 0.1 to about 0.5% of the composition.
 21. A methodaccording to claim 13 wherein the terpene comprises limonene.
 22. Amethod according to claim 1 in which the composition comprises about 0.5to 4% of polyvinyl methyl ether maleic anhydride copolymer.
 23. A methodaccording to claim 1 in which the composition comprises a toothhardening proportion of fluoride ions and an antitartar proportion of apolyphosphate or a mixture of polyphosphates.
 24. A method according toclaim 23 in which the composition comprises fluoride ions and about 0.5to 4% of polyvinyl methyl ether maleic anhydride copolymer whichtogether stabilize the polyphosphate(s) against enzymatic loss ofanti-tartar action.
 25. A method according to claim 1 wherein saidcontainer is opaque.